EP1448612B1 - Vinylaromatic polymers with improved flame resistance - Google Patents

Vinylaromatic polymers with improved flame resistance Download PDF

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Publication number
EP1448612B1
EP1448612B1 EP02791667A EP02791667A EP1448612B1 EP 1448612 B1 EP1448612 B1 EP 1448612B1 EP 02791667 A EP02791667 A EP 02791667A EP 02791667 A EP02791667 A EP 02791667A EP 1448612 B1 EP1448612 B1 EP 1448612B1
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EP
European Patent Office
Prior art keywords
weight
vinylaromatic
polymer
polymers according
mixture
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EP02791667A
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German (de)
English (en)
French (fr)
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EP1448612A1 (en
Inventor
Richard Odueyungbo
Dario Ghidoni
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Versalis SpA
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Polimeri Europa SpA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers

Definitions

  • the present invention relates to vinylaromatic polymers with improved flame resistance.
  • the present invention relates to self-extinguishing or flame-resistant vinylaromatic polymers, optionally expandable, capable of complying, for example, with the DIN 4102 regulation for expandable materials.
  • Vinylaromatic polymers and among these, polystyrene in particular, are products which have been known and used for a long time for the preparation of compact and/or expanded articles which can be used in various applicative fields, among which the most important are those relating to household appliances, transport, the building industry, office machines, etc.
  • a particularly interesting field is thermal insulation where vinylaromatic polymers are essentially used in expanded form.
  • These expanded products are obtained by swelling in a pre-expander beads of expandable polymer previously impregnated with an expanding agent and molding the swollen particles inside a closed mould by means of the contemporaneous effect of pressure and temperature.
  • the swelling of the particles is generally effected with vapour, or another gas, maintained at a temperature slightly higher than the glass transition temperature (Tg) of the polymer.
  • expanded polystyrene A particular applicative field of expanded polystyrene is that of thermal insulation in the building industry where it is generally used in the form of flat plates.
  • expanded polystyrene must also have, in addition to a low thermal conductivity, a valid flame resistance which is generally obtained with particular additives.
  • U.S. patent 4,293,656 describes a polystyrene with flame resistant properties obtained by adding to the polymer, a synergic mixture of two halogenated components, one consisting of a chloro- and/or bromo-substituted hydrocarbon, the other of a diallylether of tetrabromobisphenol A such as 2,2-bis(4-allyloxy-3,5-dibromophenyl)-propane.
  • the Applicant has now found that the addition of an organic compound, capable of generating free radicals at a temperature higher than the polymerization temperature of polystyrene, to the synergic mixture of the known art, further improves the flame-resistance properties of the polymer.
  • An object of the present invention therefore relates to vinylaromatic polymers, optionally expandable, with improved flame resistance which comprise:
  • vinyllaromatic monomer essentially refers to a product which corresponds to the following general formula: wherein R is a hydrogen or a methyl group, n is zero or an integer ranging from 1 to 5 and Y is a halogen, such as chlorine or bromine, or an alkyl or alkoxyl radical having from 1 to 4 carbon atoms.
  • vinylaromatic monomers having the general formula defined above are: styrene, ⁇ -methylstyrene, methylstyrene, ethylstyrene, butylstyrene, dimethylstyrene, mono-, di-, tri-, tetra- and penta-chlorostyrene, bromostyrene, methoxy-styrene, acetoxy-styrene, etc.
  • Preferred vinylaromatic monomers are styrene and ⁇ -methylstyrene.
  • the vinylaromatic monomers having general formula (I) can be used alone or in a mixture of up to 50% by weight with other copolymerizable monomers.
  • these monomers are (meth)acrylic acid, C 1 -C 4 alkyl esters of (meth) acrylic acid, such as methyl acrylate, methylmethacrylate, ethyl acrylate, ethylmethacrylate, isopropyl acrylate, butyl acrylate, amides and nitriles of (meth)acrylic acid such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, butadiene, ethylene, divinylbenzene, maleic anhydride, etc.
  • Preferred copolymerizable monomers are acrylonitrile and methylmethacrylate.
  • Any expanding agent capable of being englobed in the vinylaromatic polymeric matrix can be used in a combination with the vinylaromatic polymers object of the present invention.
  • Typical examples are aliphatic hydrocarbons, freon, carbon dioxide, water, etc.
  • the synergic mixture of flame-resistance additives substantially comprises three additives.
  • the first consists of a chloro- and/or bromo-substituted hydrocarbon, selected from linear, branched or cyclic paraffins containing from 5 to 20 carbon atoms and (alkyl)aromatic hydrocarbons containing from 6 to 20 carbon atoms and, optionally, one or more heteroatoms such as oxygen, nitrogen and sulfur.
  • the halogen content in these additives is equal to at least 50% by weight, preferably from 55 to 85%.
  • chloro- and/or bromo-substituted hydrocarbons examples include 1,2,5,6,9,10-hexabromocyclododecane, tetrabromo, dibenzalacetone, pentabromophenylallyl ether, pentabromomonochlorocyclohexane, 1,1,2,3,4,4-hexabromobutene-2, 2,5-bis(tribromomethyl)-1,3,4-thiadiazole, 2,4,6-tris(tribromomethyl)-1,3,5,-triazine, tetrabromoethane, bromotrichloromethane, 1,2,5,6-tetrabromohexane, hexabromobenzene, pentabromophenol, pentabromo-diphenylether, octabromocyclohexadecane, ⁇ -bromonaphthalene.
  • the bromo- and/or chloro-substituted hydrocarbon is present in a quantity equal to or higher than 10% by weight, preferably from 10 to 70%, even more preferably from 15 to 50%.
  • the additive 2,2-bis(4-allyloxy-3,5-dibromophenyl)-propane is present in the synergic mixture in a quantity lower than 70% by weight, preferably from 25 to 70%, even more preferably from 30 to 65%.
  • any organic compound capable of generating free radicals at a temperature higher than 130°C can be used as third component of the synergic mixture of flame-resistance additives, object of the present invention.
  • these additives can be selected from peroxides, percarbonates, azo derivatives or from carbon-carbon initiators.
  • the third additive of the synergic mixture is present in a quantity equal to or lower than 30% by weight, preferably from 5 to 25%, even more preferably from 7 to 20%.
  • the expanding agent (b), if present, and the synergic mixture (c) are preferably added to the vinylaromatic polymer during the polymerization phase.
  • a polymer is obtained which, if expanding agents are added, can be transformed to produce expanded articles having a density ranging from 5 to 50 g/l, preferably from 10 to 25 g/l, with an excellent thermal insulation capacity.
  • These materials moreover, have a flame-resistance property which passes the DIN 4102 test.
  • a further object of the present invention relates to the process for the preparation of vinylaromatic polymers, optionally expandable, with improved flame-resistance.
  • a further object of the present invention relates to a process for preparing vinylaromatic polymers, optionally expandable, which comprises polymerizing in an aqueous suspension one or more vinylaromatic monomers, optionally together with at least one polymerizable comonomer in a quantity of up to 50% by weight, in the presence of a synergic mixture of flame-resistance additives comprising a chloro- and/or bromo-substituted hydrocarbon, 2,2-bis(4-allyloxy-3,5-dibromophenyl)-propane and an organic compound capable of generating free radicals at a temperature higher than 130°C, and from 0 to 10% by weight of an expanding agent added before, during or after the end of the polymerization.
  • a synergic mixture of flame-resistance additives comprising a chloro- and/or bromo-substituted hydrocarbon, 2,2-bis(4-allyloxy-3,5-dibromophenyl)-
  • substantially spherical polymer beads are obtained, with an average diameter ranging from 0.2 to 2 mm, inside which the synergic mixture is homogeneously dispersed.
  • polymerization additives typically used for producing vinylaromatic polymers, are adopted, such as polymerization catalysts, stabilizing agents of the suspension, chain transfer agents, expanding aids, nucleating agents, plasticizers, mineral fillers, etc.
  • mineral fillers of athermane materials such as graphite, or refracting materials, such as titanium dioxide, during the polymerization, in a quantity ranging from 0.05 to 25% by weight, calculated with respect to the resulting polymer.
  • the expanding agents are preferably added during the polymerization phase and are selected from aliphatic or cycloaliphatic hydrocarbons containing from 3 to 6 carbon atoms such as n-pentane, isopentane, cyclopentane or their mixtures; the halogenated derivatives of aliphatic hydrocarbons containing from 1 to 3 carbon atoms such as, for example, dichlorodifluoromethane, 1,2,2-trifluoroethane, 1,1,2-trifluoroethane; carbon dioxide and water.
  • a solution of vinylaromatic polymer in the monomer, or mixture of monomers in which the concentration of polymer ranges from 1 to 30% by weight, preferably from 5 to 20%.
  • the solution can be obtained either by diluting a preformed polymer (for example fresh polymer or the waste products of previous polymerizations and/or expansions) in the monomer or by pre-polymerizing the monomer, or mixture of monomers, in mass, in order to obtain the above concentrations, and then continuing the polymerization in aqueous suspension in the presence of the remaining additives.
  • Another object of the present invention relates to a process for preparing in mass and in continuous, vinylaromatic polymers, optionally expandable, which comprises the following steps in series:
  • EBCD hexabromine-cyclododecane
  • BE 2,2-bis(4-allyloxy-3,5-dibromophenyl)-propane
  • DCP dicumyl peroxide
  • the beads of expandable polymer thus produced are subsequently recovered, washed with deionized water, dried in a stream of warm air, 0.02% of ethoxylated amine are added, and screened separating the fraction with a diameter ranging from 1 to 1.5 mm.
  • the beads are expanded with vapour to a temperature of 100°C and subsequently moulded to give simple end-products with a density of about 16-17 g/l.
  • Test samples according to the regulation DIN 4102 are taken from the end-products. These test samples are then conditioned in an oven up to the maximum expanding content of 0.5%. The results of the flame test are indicated in the table.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP02791667A 2001-11-30 2002-11-06 Vinylaromatic polymers with improved flame resistance Expired - Lifetime EP1448612B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITMI20012515 2001-11-30
ITMI20012515 ITMI20012515A1 (it) 2001-11-30 2001-11-30 Polimeri vinilaomatici a migliorati comportamento al fuoco
PCT/EP2002/012474 WO2003046016A1 (en) 2001-11-30 2002-11-06 Vinylaromatic polymers with improved flame resistance

Publications (2)

Publication Number Publication Date
EP1448612A1 EP1448612A1 (en) 2004-08-25
EP1448612B1 true EP1448612B1 (en) 2008-12-31

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ID=11448642

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EP02791667A Expired - Lifetime EP1448612B1 (en) 2001-11-30 2002-11-06 Vinylaromatic polymers with improved flame resistance

Country Status (6)

Country Link
EP (1) EP1448612B1 (es)
AU (1) AU2002358002A1 (es)
DE (1) DE60230658D1 (es)
ES (1) ES2320428T3 (es)
IT (1) ITMI20012515A1 (es)
WO (1) WO2003046016A1 (es)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4787160B2 (ja) 2003-10-01 2011-10-05 チバ ホールディング インコーポレーテッド 難燃性組成物
DE102004034516A1 (de) 2004-07-15 2006-02-16 Basf Ag Verfahren zur Herstellung von flammgeschütztem, expandierbarem Polystyrol
EP2062935B1 (de) 2007-11-21 2012-04-18 Basf Se Verfahren zur Einbringung von Feststoffpartikeln in Polymerschmelzen
KR101578953B1 (ko) 2007-11-21 2015-12-18 바스프 에스이 난연성 팽창성 스티렌 중합체 및 이의 제조 방법

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3058926A (en) * 1958-07-24 1962-10-16 Dow Chemical Co Method for making self-extinguishing alkenyl aromatic resin compositions comprising incorporating therein an organic bromine-containing compound and an organic peroxide
DE2950098A1 (de) * 1979-12-13 1981-07-09 Basf Ag, 6700 Ludwigshafen Flammgeschuetzte styrolpolymerisate

Also Published As

Publication number Publication date
EP1448612A1 (en) 2004-08-25
ES2320428T3 (es) 2009-05-22
AU2002358002A1 (en) 2003-06-10
ITMI20012515A1 (it) 2003-05-30
DE60230658D1 (de) 2009-02-12
WO2003046016A1 (en) 2003-06-05

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